Organic antimony compounds and process of making same.



UNITED STATES PAtrENr OFFICE.

LUDWIG KAUFMANN, F BERLIN, GERMANY.

ORGANIC ANTIMONY COMPOUNDS AND PROCESS OF MAKING SAME.

1,060,765. No Drawing.

To all whom it may concern:

Be it known that I, LUDWIG\I{AUFJ\IANN, chemist, citizen of Germany, subject of the King of Bavaria and of the Emperor of Germany, residing at Berlin, in the Kingdom of Prussia and Empire of Germany, have invented new and useful Organic Antimony Com )ounds and Process of Making Some, of which the following is a specification. e

' The subject matter of my invention is a process of prodnein tri henylstibin sultid,

1tshomol0gues,and their erivatives. It also comprises the chemical compounds obtained thereby. These compounds readily tend to decompose or split by giving oil their sulfur. They are to be used as therapeutical agents durin'g employment. Experiments have shown that the sulfur split off in this manner and therefore acting in statu mtscendz' on the human body has a far more intensive action for instance against dernintoses than the usual ,sulfur containing medicaments. A decom osition being achieved in this sense can be 0 served in the triphenylstibin sulfid, discovered by me arid having the formula (Q asbs.

have attempted to could obtain the sulhd by introducing sul-' fureted hydrogen into the alcoholic ummoniacal solution of the 't-ri'phenlystibin haloids, but as the result of their experiments they obtained only a reduction of the haloid compounds to triphenylstibin so that they were induced to give to the reaction the following equation i But according to in observation the reaction by no means ta es place in this simple manner. Namely, if the sulfureted hydrogen is introduced cautiously, white crystalline needles are firstly precipitated which do not melt-together, as Michaelis and Reese state, but redissolve when more sulfureted hydrogen is introduced, the liquid simultaneously coloring an intense yellowish red. The crystals which first appear and which were talren by Michaelis and Reese for triphenylstibin are,'a,ccordirig to analysis, noth- Specification of Letters Patent. Application filed August 14, 1909. Serial No. 512,849.

ing else than triphen lstibin sulfid, whereas, it is true, only tripiienylstibin can be obtained from the yellowish red solution in accordance to the statements of these authors. In explaining the reaction which certainly occurs in several successive phases it must first be stated that in the alcoholic ammoniacal solution the chlorides such is no longer present. On the other hand it can be shown that the solution contains the hydroxid. (C lI ),,Sb(OH) or its alcoholate If for simplicity it'is supposed that the hydroxid is contained in the solution, the first phase of the sulfureted hydrogen action can be expressed bythe following equation:

(QJ M M )2+ 2 i (C,,H,),SbS+2H O. This transformation takes places quantitatively, and only when the nntimon compound has been transformed into t e sulfid difiicultly soluble in alcohol and when more sulfuretcd hydrogen is introduced does dissolution take place, the commencement of which 'is very clearly characterized by the occurrence of a yellow coloration. Michaelis Patented May c, 1913. i

and Reese explained this coloration by asr suming that the sulfur which in their opinion is split off (comp. the last formula but one) dissolves in the ammonium sulfid to ammonium poly-sulfid. This assumption is not correct because the yellow solution when left to itself becomes perfectly colorless after some tin1e,,sulfur being precipitated. Also, thc decolorizcdsolution yields no cupric sulfid withsulfate of copper. Consequently, the yellow coloration can only be attributed to the antimony compound formcrl from the sulfid and dissolved in alcohol. It has not been possible heretofore to isolate this compound from the solution. process, however, it will scarcely be possible to take anything else into consideration than either-according to the analog of the solubility of the sulfids of antimony in am- For the explanation of the dissolvingmonium su1iid -the production of a sulfo c,n. ,sn=s:s Obviously, the last formula recalls the type of diazo compounds, and indeed a somewhat far reaching analogy (color of the solutions, instability of the same, decompo sition with splitting ofi of sulfur corresponding to the splitting off of nitrogen in the diazo compounds) is not to be denied.

With regard to decomposition, this takes place when the solutions are left to themselves for some time or when they are inspissated in vacuo. If a solution of-the triphenylstibin sulfid be made in alcoholic ammonium sulfid .in such a manner that there remains sulfid still undissolved an excess of ammonium s'ulfid is avoided. If this solution be filtered and allowed to decompose by being left to itself, after the sulfur has been filtered off there is neither sulfureted hydrogen nor ammonium sultid 'in it, as no cupric sulfid-is precipitated by an addition of sulfate of copper, as already mentioned; but it has reducing-properties since metallic silver is precipitated from an alcoholic solution of silver nitrate. The decomposed colorless solution-separated from the sulfur, when inspissated in the vacuum exsiccator, as residue leaves pure triphenylstibin. Lastly, it may be stated that the yel low solutions containing the complex anti mony compounds are atonce decolorized when mixed with an .alcoholicammoniacal solution of stibin haloid, stibin sulfid being precipitated in this case.

The complex antimony compound distinguished by the above described properties consequently causes'the second phase of the action of the sulfureted hydrogen conimencing with the yellow coloration. In the following third phase of reaction the repeatedly described splitting oil of triphenylstibin takes place. As follows from the above description of the course of -the reaction, the individual phases of the action of the sulfureted hydrogen can be kept well apart. Consequently it is perfectly possible to use the reaction for producing triphenylstibin or triphenylstibin sulfid, In the former case the directions according to Michaelis and Reese (loc. cit. p. 42 it.) are followed, the process being allowed to run through all three phases.- For producing triphenylstibin sultid the reaction is broken ofi after the first phase. For obtaining an almost quantitative yield l. proceed as follows: 10 g. of the triphenylstibin haloid compound,-prctcrably the bromin compound is used as this can he made very conveniently (comp. Michaclis and Reese loc. cit. p. 50)-arc dissolved at the temperature of the room in 160 ccms. of a cold-saturated alcoholic ammonia solution. The alcohol used for this cold saturated ammonia s0- lulion is absolute, about 99%. A uniform, puriiied current of 'suli'urclcd hydrogen is iulrorhua-dinto the filtered solution while constantly agitating.- This introduction is crystalline paste produced is sucked dry,

washed witlralcohol and dried on clay.

The yield amount toapprox. 6 g., 2'. 6., of the theoretical amount. The almost perfectly pure product can be obtained in beautit'ul needles by recrystallizing from alcohol. instead of the brom-in compounds, I can chloriu compounds taking care that the solutions which contain the arylstibin compounds and from which the sultid is obtained by introducing sulphureted hydrogen are as concentrated as possible. -For this purpose I proceed in such manner thatthe haloid compounds, that is to say the arylstis bin chlori ds, are decomposed with much less saturated alcoholic ammonia solution and at the boiling point. Y

In the case of triphenylstibin chlorid I ust as wellproee'ed from the much cheaper pour over 10 g. of this compound 7 O ccms. of

the alcoholic ammonia solution, boil for one hour in a flask with a return condenser, leave it to itself approx. two hours, filter off the precipitated ammonium chlorid, and intro I 'The yield here also is approx. 80' of the theoretical"amount. Moreover the sulfid can be made in analogous manner, also contrary to the statements of Michaelis and Reese (Zoo. cit. ,p. 53), by adding alcoholic ammonium sulfid to the alcoholic ammoniacal solution of the bromid. Here also the precaution must be'taken that an excess of ammonium sulfid causing the sulfid' produced to be dissolved be avoided.

In spite of its near relation to antimony sulfid triphcnylstibin sulfid is pure white in color. Itmells exactly at 119 to 120 cent. and decomposes at approx. 200 cent. leav-' ing a red residue. It dissolves readily in benzene. chloroform and glacial acetic acid,

with more ditliculty inaleohol (1 part in parts absolute alcohol at ordinary temperature, in 100 parts at boiling temperature), and with great diliiculty in ether and petrolcthcr. When the solutions are heated fora somewhat long time a gradual decomposilion into triphcnylslihiu and sulfur occurs. This can also be caused by the action of dilute acids, crcu acetic acid. It is yet to be l'cinarked. that the sulfid is soluble neither in alcoholic aunnonia nor in alcoholic sulfurcted hydrogen. whereas it is very readily dissolved y an alcoholic solution of ammo llllllll sullid forming a \'cllo\-;-rcd solution, the properties of which are described herein before.

'lhe sulfur of the stibin sullid compounds larly by powdered coppcr.

- halogen compounds of its homologues, and

their derivatives and instead of the halogenized products also the hydroxid compounds otherwise formed as intermediate products.

and generally speaking every organic sti bin compound containing aromatic radicals and a group to be substituted by sulfur may be used as starting products. Instead of the sulfureted hydrogen another sulfur compound inclining to'give off its sulfur may be employed.

Having nowparticularl'y described. and ascertained the nature of my and in what manner the same is to be performed, I declare that what I claim is:

1. A process of producing stibin sulfids containing aromatic radicals which consists in causing a sulfur compound to react on an organic stibin compound containing aromatic radicals and a group to be substituted by sulfur and avoiding excess of the sulfurizing compound.

'2. A process of producing triarylstibin sulfids, consisting in reacting on a halogensaid invention ized triarylstibin with sulfureted hydrogen, avoiding an excess of the hydrogen sulfid.

3. The herein described new compounds being sulfids of arylstibins of the following general formula:

Y SbS in which Y represents three aromatic radicals.

4. The herein described new compound, triphenylstibin sulfid of the following formula:

the new compound being a white cristallic body melting at 119 to 120 Cent. easily soluble in benzene, chloroform and glacial acetic acid and being split up into triphenylstibin and sulfur on heating and by the action of diluted acids.

In testimony whereof I have hereunto set my hand in prcsenceof two subscribing witmesses.

LUDWIG KAUFMANN. Witnesses HENRY HASPER, ARTHUR SCHROEDER. 

